U.S. patent number 9,440,420 [Application Number 14/124,477] was granted by the patent office on 2016-09-13 for polyurethane polymers.
This patent grant is currently assigned to Covestro Deutschland AG. The grantee listed for this patent is Mathias Matner, Evelyn Peiffer. Invention is credited to Mathias Matner, Evelyn Peiffer.
United States Patent |
9,440,420 |
Peiffer , et al. |
September 13, 2016 |
Polyurethane polymers
Abstract
The present invention relates to polyurethane polymers, a
process for their preparation and their use as binders for
adhesives, coatings or foams.
Inventors: |
Peiffer; Evelyn (Leverkusen,
DE), Matner; Mathias (Neuss, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Peiffer; Evelyn
Matner; Mathias |
Leverkusen
Neuss |
N/A
N/A |
DE
DE |
|
|
Assignee: |
Covestro Deutschland AG
(DE)
|
Family
ID: |
46208087 |
Appl.
No.: |
14/124,477 |
Filed: |
June 5, 2012 |
PCT
Filed: |
June 05, 2012 |
PCT No.: |
PCT/EP2012/060592 |
371(c)(1),(2),(4) Date: |
January 16, 2014 |
PCT
Pub. No.: |
WO2012/168236 |
PCT
Pub. Date: |
December 13, 2012 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
|
US 20140120354 A1 |
May 1, 2014 |
|
Foreign Application Priority Data
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Jun 8, 2011 [DE] |
|
|
10 2011 077 213 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
18/632 (20130101); C09D 175/04 (20130101); C09J
175/04 (20130101); C08G 18/63 (20130101); B32B
27/40 (20130101); C08G 18/718 (20130101); C08G
18/409 (20130101); Y10T 428/31551 (20150401) |
Current International
Class: |
B32B
27/40 (20060101); C09J 175/04 (20060101); C08G
18/71 (20060101); C09D 175/04 (20060101); C08G
18/40 (20060101); C08G 18/63 (20060101) |
Field of
Search: |
;428/423.1 ;521/154
;524/588 ;528/29 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1 745 526 |
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Mar 1972 |
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DE |
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2638759 |
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Mar 1978 |
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DE |
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19908562 |
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Oct 1999 |
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DE |
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102007058344 |
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Jun 2009 |
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DE |
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102008038488 |
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Feb 2010 |
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DE |
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0008444 |
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Mar 1980 |
|
EP |
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0070475 |
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Jan 1983 |
|
EP |
|
0250351 |
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Dec 1987 |
|
EP |
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0372561 |
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Jun 1990 |
|
EP |
|
0 397 036 |
|
Nov 1990 |
|
EP |
|
0654302 |
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May 1995 |
|
EP |
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0732348 |
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Sep 1996 |
|
EP |
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1093482 |
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Apr 2001 |
|
EP |
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1136495 |
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Sep 2001 |
|
EP |
|
1505082 |
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Feb 2005 |
|
EP |
|
1541606 |
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Jun 2005 |
|
EP |
|
1671994 |
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Jun 2006 |
|
EP |
|
1924621 |
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May 2008 |
|
EP |
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1995261 |
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Nov 2008 |
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EP |
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2046861 |
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Apr 2009 |
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EP |
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WO-2007025668 |
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Mar 2007 |
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WO |
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WO2008/013731 |
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Jan 2008 |
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WO |
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Other References
International Search Report for PCT/EP2012/060592 mailed Sep. 20,
2012. cited by applicant .
International Preliminary Report on Patentability for
PCT/EP2012/060592.mailed 2013. cited by applicant .
International Preliminary Report on Patentability in English for
PCT/EP2012/060592, date of issuance Dec. 10, 2013. cited by
applicant .
U.S. Appl. No. 14/124,487, filed Dec. 6, 2013, Peiffer et al. cited
by applicant.
|
Primary Examiner: Tran; Thao T
Attorney, Agent or Firm: Drinker Biddle & Reath LLP
Claims
The invention claimed is:
1. An adhesive composition comprising 5 wt. % to 100 wt. % of an
alkoxysilane group-modified polymer or of a mixture of two or more
such polymers modified with alkoxysilane groups wherein the polymer
is obtained by reacting a) compounds or mixtures of compounds
having isocyanate-reactive groups, which comprise at least 5 wt. %
of organic filler dispersed therein, with b) an
isocyanate-functional alkoxysilane compound of the general formula
(I): ##STR00002## wherein Z.sub.1, Z.sub.2, and Z.sub.3 are
identical or different C.sub.1-C.sub.8-alkoxy or
C.sub.1-C.sub.8-alkyl radicals, which 10 can also be bridged, but
wherein at least one C.sub.1-C.sub.8-alkoxy radical must be present
on each Si atom, Q is an at least difunctional linear or branched
organic radical and wherein the polymer has a viscosity at
23.degree. C. of 13.8 Pas or less, 0 wt. % to 50 wt. % of a
plasticizer/flameproofing agent or of a mixture of two or more
plasticizers/flameproofing agents, 0 wt. % to 95 wt. % of a
solvent/blowing agent or of a mixture of two or more
solvents/blowing agents, 0 wt. % to 20 wt. % of a moisture
stabilizer or of a mixture of two or more moisture stabilizers, 0
wt. % to 5 wt. % of an antiageing agent or of a mixture of two or
more antiageing agents, 0 wt. % to 5 wt. % of a catalyst or of a
mixture of two or more catalysts, 0 wt. % to 80 wt. % of a filler
or of a mixture of two or more fillers and the adhesive has a
tensile shear strength of greater than 10 N/mm.sup.2.
2. The adhesive composition according to claim 1, wherein Q is an
alkylene radical having 1 to 8 carbon atoms.
3. The adhesive composition according to claim 1, wherein the
compounds or mixtures of compounds having isocyanate-reactive
groups in part (a) comprise polyether polyols.
4. The adhesive composition according to claim 1, in which part a)
comprises at least 20 wt. % of dispersed organic filler.
5. The adhesive composition according to claim 1, in which part a)
comprises at least 15 wt. % of dispersed organic filler.
6. The adhesive composition according to claim 1, in which part a)
comprises at least 10 wt. % of dispersed organic filler.
7. The adhesive composition according to claim 1, wherein the
polymer has a viscosity at 23.degree. C. of less than 10 Pas.
8. The adhesive composition according to claim 1, wherein the
polymer had a viscosity at 23.degree. C. of less than 5 Pas.
9. The adhesive composition according to claim 1, wherein the
isocyanate-functional alkoxysilane compound has a molecular weight
of from 140 g/mol to 500 g/mol.
10. The adhesive composition according to claim 1, wherein the
isocyanate-functional alkoxysilane compound is
isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane,
(isocyanatomethyl)-methyldimethoxysilane,
(isocyanatomethyl)methyldiethoxysilane,
3-isocyanatopropyl-trimethoxysilane,
3-isocyanatopropylmethyldimethoxysilane,
3-isocyanatopropyltriethoxysilane and
3-isocyanatopropylmethyldiethoxysilane.
11. The adhesive composition according to claim 1, wherein the
isocyanate-functional alkoxysilane compound is
3-isocyanatopropyltrimethoxysilane.
12. The adhesive composition according to claim 6, wherein the
isocyanate-functional alkoxysilane compound is
3-isocyanatopropyltrimethoxysilane.
13. A substrate coated with the adhesive according to claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C.
.sctn.371) of PCT/EP2012/060592, filed Jun. 5, 2012, which claims
benefit of German application 10 2011 077 213.8, filed Jun. 8,
2011.
The present invention relates to non-aqueous polyurethane polymers,
a process for their preparation and their use as binders for
adhesives, coatings or foams.
Alkoxysilane-functional polyurethanes which crosslink via a silane
polycondensation have been known for a long time. An overview
article on this subject is to be found e.g. in "Adhesives Age"
April 1995, page 30 et seq. (authors: Ta-Min Feng, B. A. Waldmann).
Such alkoxysilane-terminated moisture-curing one-component
polyurethanes are increasingly being used as flexible coating,
sealing and adhesive compositions in the building industry and in
the automobile industry.
According to U.S. Pat. No. 3,627,722 or DE-A 1 745 526, such
alkoxysilane-functional polyurethanes can be prepared by e.g.
reacting polyether polyols with an excess of polyisocyanate to give
an NCO-containing prepolymer, which is then in turn reacted further
with an amino-functional alkoxysilane.
EP-A 0 397 036, DE-A 19 908 562 (corresponds to EPA 1 093 482) and
US-A 2002/0100550 describe further different routes for the
preparation of alkoxysilane-terminated polymers. According to these
publications, in each case high molecular weight polyethers having
an average molecular weight of 4,000 g/mol or higher are
employed.
EP-A 0 070 475 describes the preparation and use of
alkoxysilane-terminated polymers starting from hydrogen-acid
prepolymers by termination with NCO-functional alkoxysilanes.
Polyols having a molecular weight of 500-6,000 g/mol are used for
the prepolymer synthesis. The polymers described therein are
employed as binders in sealant formulations, that is to say
flexible systems.
An analogous process is described in the application DE-A 10 2007
058 344.
The possibility of arriving at prepolymers of particularly low
viscosity by using isocyanate-functional alkoxysilane units is
disclosed inter alia in U.S. Pat. No. 4,345,053. In this, an
OH-functional prepolymer is terminated by an isocyanate-functional
alkoxysilane, which in the end means the saving of one urea group
per termination. Nevertheless, the OH-functional prepolymer still
comprises urethane groups which result from the prelengthening of a
polyether polyol with diisocyanate. As is likewise disclosed in
EP-A 0 372,561, these can be saved by employing specially prepared
long-chain polyethers having a low degree of unsaturation and
polydispersity. Nevertheless, in the stoichiometric reaction of
such isocyanate-functional alkoxysilane units binders are obtained
which, because of inadequate masking, above all if very long-chain
polyethers are used, cannot crosslink adequately during curing.
This leads to very soft polymers having a high surface tackiness
and a lack of resilience, or a high plastic deformability.
EP-A 1 924 621 (corresponds to WO2007025668) describes the
preparation and use of alkoxysilane-terminated polymers starting
from polyether polyols by termination with NCO-functional
alkoxysilanes. Polyols having a molecular weight of 3,000-20,000
g/mol are used for the synthesis. The polymers described therein
are employed as binders in sealant formulations, that is to say
flexible systems.
All of these alkoxysilane-terminated systems form, after curing,
flexible polymers having a relatively low strength and a high
elongation at break. DE-A 1 745 526 describes tensile strengths in
the range of from 3.36 kg/cm.sup.2 to 28.7 kg/cm.sup.2 for
polyoxypropylene glycol-based polymers. Only with crystallizing
polycaprolactones are high strengths which are adequate for
structural gluings achieved.
However, these systems have the disadvantage that they are very
highly viscous or even solid at room temperature and therefore can
only be processed hot.
The field of use of the abovementioned applications is accordingly
limited on the one hand to sealants and flexible adhesives and on
the other hand to highly viscous or solid systems, which can only
be processed hot.
The present invention was therefore based on the object of
providing non-aqueous, alkoxysilane-terminated polymers which are
liquid at room temperature and achieve a high cohesive strength
when cured, so that adhesives which render possible structural
gluing can be formulated using them.
It has now been found that such alkoxysilane-terminated polymers
having the required properties can be prepared by using polymer
polyols having organic fillers dispersed therein and reacting these
with an isocyanate-functional alkoxysilane.
The invention therefore provides polymers modified with
alkoxysilane groups, which are obtainable by reaction a) of
compounds or mixtures of compounds having isocyanate-reactive
groups which comprise at least 5 wt. % of organic filler dispersed
therein with b) an isocyanate-functional alkoxysilane compound of
the general formula (I):
##STR00001## wherein Z.sup.1, Z.sup.2 and Z.sup.3 are identical or
different C.sub.1-C.sub.8-alkoxy or C.sub.1-C.sub.8-alkyl radicals,
which can also be bridged, but wherein at least one
C.sub.1-C.sub.8-alkoxy radical must be present on each Si atom, Q
is an at least difunctional linear or branched organic radical,
preferably an alkylene radical having 1 to 8 carbon atoms.
In this context, the reaction of b) with a) can preferably be
carried out in a ratio of from 0.8:1.0 to 1.5:1.0
(NCO:isocyanate-reactive hydrogen).
The compounds according to the invention are non-crystallizing
substances which are liquid at room temperature.
All the polymer polyols having organic fillers dispersed therein
which are known to the person skilled in the art can be used as
part a). Such polymer polyols can be both polyester and polyether
polyols. Preferably, polyether polyols having organic fillers
dispersed therein, such as, for example, addition products of
toluylene-diisocyanate with hydrazine hydrate (PHD), as described
in DE-A 2 638 759, U.S. Pat. No. 4,089,835 or U.S. Pat. No.
4,260,530, or copolymers of styrene and acrylonitrile (SAN), as
described in U.S. Pat. No. 7,179,882, EP-A 0 008 444 or U.S. Pat.
No. 4,895,878, are employed. Polyester polyols having organic
fillers dispersed therein are described in EP-A 1 505 082, EP-A 1
541 606, EP-A 1 671 994, EP-A 0 250 351, U.S. Pat. No.
3,294,711.
Part a) comprises at least 5 wt. % of dispersed organic filler,
preferably at least 10 wt. % of dispersed organic filler,
particularly preferably at least 20 wt. % of dispersed organic
filler.
In addition to the polymer polyols having organic fillers dispersed
therein, all the compounds known to the person skilled in the art
which have isocyanate-reactive groups can also be employed as a
proportion of part a). These can be, for example, low molecular
weight, multifunctional, isocyanate-reactive compounds, such as
aliphatic polyols, polythiols or polyamines, aromatic polyols,
polythiols or polyamines, or can be higher molecular weight
isocyanate-reactive compounds, such as polyether polyols, polyether
amines, polycarbonate polyols, polyester polyols and polythioether
polyols. Preferably, such isocyanate-reactive compounds have an
average functionality of from 1 to 6, preferably 2 to 3.5 and
particularly preferably from 2 to 3.
Preferably, part a) has on average a functionality of at least
2.0.
Alternatively, isocyanate-reactive polyurethane polymers such as
are described, for example, in EP-A 0 070 475 and DE-A 10 2007 058
344 can be employed in part a), optionally also as a
proportion.
In principle all monoisocyanates comprising alkoxysilane groups and
having a molecular weight of from 140 g/mol to 500 g/mol are
suitable as isocyanate-functional alkoxysilane compounds of the
general formula (I). Examples of such compounds are
isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane,
(isocyanatomethyl)methyldimethoxysilane,
(isocyanatomethyl)methyldiethoxysilane,
3-isocyanatopropyltrimethoxysilane,
3-isocyanatopropylmethyldimethoxysilane,
3-isocyanatopropyltriethoxysilane and
3-isocyanatopropylmethyldiethoxysilane. The use of
3-isocyanatopropyltrimethoxysilane is preferred here.
According to the invention it is also possible to use
isocyanate-functional silanes which have been prepared by reaction
of a diisocyanate with an amino- or thiosilane, such as are
described in U.S. Pat. No. 4,146,585 or EP-A 1 136 495.
The reaction of b) with a) is preferably carried out in a ratio of
from 0.8:1.0 to 1.5:1.0 (NCO:isocyanate-reactive hydrogen),
particularly preferably in a ratio of from 1.0:1.0 to 1.5:1.0, very
particularly preferably in a ratio of from 1.0:1.0 to 1.2:1.0.
Preferably, the isocyanate is employed in an equimolar amount or in
excess, such that the resulting polymers according to the invention
are completely alkoxysilane-terminated. If necessary, the optimum
ratio for a specific substance combination of b) and a) is to be
determined by orientating preliminary experiments, which is a
conventional procedure for the person skilled in the art.
If the ratios of amounts are chosen such that after the reaction of
a) with b) has been carried out free NCO groups remain, these can
then be taken up by reaction with compounds which are reactive
towards isocyanates or by allophanation, as described, for example,
in EP-A 1 924 621.
The reaction of part a) with part b) is preferably carried out in a
temperature range of from 20.degree. C. to 200.degree. C.,
particularly preferably within from 40.degree. C. to 120.degree. C.
and particularly preferably from 60.degree. C. to 100.degree.
C.
This reaction can be accelerated by catalysis. Urethanization
catalysts known per se to the person skilled in the art, such as
organotin compounds or aminic catalysts, are possible for the
acceleration. Organotin compounds which may be mentioned by way of
example are: dibutyltin diacetate, dibutyltin dilaurate, dioctyltin
dilaurate, dibutyltin bis-acetoacetonate and tin carboxylates, such
as, for example, tin octoate. The tin catalysts mentioned can
optionally be used in combination with aminic catalysts, such as
aminosilanes or 1,4-diazabicyclo[2.2.2]octane.
Dibutyltin dilaurate is particularly preferably employed as the
catalyst.
The reaction is continued until complete conversion of the
isocyanate-reactive groups is achieved. The course of the reaction
is appropriately monitored by checking the NCO content and is ended
when the NCO content has fallen to <1 wt. %. This can be
monitored by suitable measuring equipment installed in the reaction
vessel and/or with the aid of analyses on samples taken. Suitable
methods are known to the person skilled in the art. They are, for
example, viscosity measurements, measurements of the NCO content,
the refractive index or the OH content, gas chromatography (GC),
nuclear magnetic resonance spectroscopy (NMR), infra-red
spectroscopy (IR) and near infra-red spectroscopy (NIR).
Preferably, the NCO content of the mixture is determined
titrimetrically.
It is irrelevant whether the process is carried out continuously,
e.g. in a static mixer, extruder or kneader, or discontinuously,
e.g. in a stirred reactor.
The process is preferably carried out in a stirred reactor.
The invention also provides adhesives, coatings or foams based on
the polymers according to the invention. These adhesives, coatings
or foams crosslink under the action of moisture from the atmosphere
via a silanol polycondensation. Preferably, the polymers according
to the invention are employed in foams and adhesives, particularly
preferably in adhesives which, according to the measurement method
described in the experimental part, have a tensile shear strength
of at least 10 N/mm.sup.2.
For the preparation of such adhesives, coatings and foams, the
polymers according to the invention comprising alkoxysilane end
groups can be formulated by known processes together with
conventional solvents, blowing agents, plasticizers, fillers,
pigments, flameproofing agents, desiccants, additives, light
stabilizers, antioxidants, thixotropy agents, catalysts, adhesion
promoters and optionally further auxiliary substances and
additives.
Typical foams and adhesive and coating preparations according to
the invention comprise, for example, 5 wt. % to 100 wt. % of a
polymer modified with alkoxysilane groups, according to claim 1, or
of a mixture of two or more such polymers modified with
alkoxysilane groups, up to 50 wt. % of a plasticizer/flameproofing
agent or of a mixture of two or more plasticizers/flameproofing
agents, up to 95 wt. % of a solvent/blowing agent or of a mixture
of two or more solvents/blowing agents, up to 20 wt. % of a
moisture stabilizer or of a mixture of two or more moisture
stabilizers, up to 5 wt. % of one or more antiageing agents, up o 5
wt. % of a catalyst or of a mixture of two or more catalysts and up
to 80 wt. % of a filler or of a mixture of two or more fillers.
Suitable plasticizers which may be mentioned by way of example are
phthalic acid esters, adipic acid esters, alkylsulfonic acid esters
of phenol, phosphoric acid esters or also higher molecular weight
polypropylene glycols.
Flameproofing agents which can be employed are the typical halogen-
or phosphorus-containing compounds, and likewise inorganic
flameproofing agents, such as, for example, aluminium oxide
hydrate.
In the simplest case, air or nitrogen can be employed as a blowing
agent, but all other blowing agents known per se from polyurethane
chemistry can of course also be employed for foaming the
composition according to the invention. Examples which may be
mentioned are n-butane, i-butane, propane and dimethyl ether, as
well as mixtures of the abovementioned agents.
Desiccants which may be mentioned are, in particular, alkoxysilyl
compounds, such as vinyltrimethoxysilane, methyltrimethoxysilane,
i-butyltrimethoxysilane, hexadecyltrimethoxysilane.
Suitable fillers which may be mentioned by way of example are
carbon black, precipitated silicas, pyrogenically produced silicas,
mineral chalks and precipitated chalks or also fibrous fillers.
Thixotropy agents which may be mentioned by way of example are
pyrogenically produced silicas, polyamides, hydrogenated castor oil
secondary products or also polyvinyl chloride.
Suitable catalysts which can be employed for curing of the
adhesives, coatings or foams according to the invention are all the
organometallic compounds and aminic catalysts which are known to
promote silane polycondensation. Particularly suitable
organometallic compounds are, in particular, compounds of tin and
of titanium. Preferred tin compounds are, for example: dibutyltin
diacetate, dibutyltin dilaurate, dioctyltin maleate and tin
carboxylates, such as, for example, tin(II) octoate or dibutyltin
bis-acetoacetonate. The tin catalysts mentioned can optionally be
used in combination with aminic catalysts, such as aminosilanes or
1,4-diazabicyclo[2.2.2]octane. Preferred titanium compounds are,
for example, alkyl titanates, such as diisobutyl-bisacetoacetic
acid ethyl ester titanate. Aminic catalysts which are suitable for
sole use are, in particular, those which have a particularly high
base strength, such as amines having an amidine structure.
Preferred aminic catalysts are therefore, for example,
1,8-diazabicyclo[5.4.0]undec-7-ene or
1,5-diazabicyclo[4.3.0]non-5-ene. Bronstedt acids may also catalyse
the silane condensation. All acids which are compatible with the
particular formulation can be employed. There are mentioned here by
way of example p-toluenesulphonic acid, dodecylbenzenesulphonic
acid or also citric acid.
Adhesion promoters which are employed are the known functional
silanes, such as, for example, aminosilanes of the abovementioned
type, but also N-aminoethyl-3-aminopropyltrimethoxy- and/or
N-aminoethyl-3-aminopropylmethyldimethoxysilane, epoxysilanes
and/or mercaptosilanes.
The following examples illustrate the present invention without
limiting it.
EXAMPLES
Unless stated otherwise, all the percentage data relate to percent
by weight (wt. %).
The ambient temperature of 23.degree. C. prevailing at the time the
experiments were carried out is called RT (room temperature).
The methods described below for the determination of the
corresponding parameters were used for carrying out and evaluating
the examples and are also the methods in general for determination
of the parameters relevant according to the invention.
Determination of the Isocyanate Content
The determination of the NCO contents in wt. % was carried out in
accordance with DIN EN ISO 11909 by back-titration with 0.1 mol/l
of hydrochloric acid after reaction with butylamine.
Determination of the Viscosity
The viscosity measurements were carried out in accordance with
ISO/DIN 3219:1990 at a constant temperature of 23.degree. C. and a
constant shear rate of 250/sec using a plate-cone rotary viscometer
of the Physica MCR type (Anton Paar Germany GmbH, Ostfildern, DE)
using the CP 25-1 measuring cone (25 mm diameter, 1.degree. cone
angle).
Example 1
According to the Invention
In a 2 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 732.3 g of polypropylene glycol having a hydroxyl
number of 89 mg of KOH/g and having 20 wt. % of SAN dispersed
therein, and 0.05 g of dibutyltin dilaurate (Desmorapid.RTM. Z,
Bayer MaterialScience AG) were heated to 60.degree. C. 267.8 g of
3-isocyanatopropyltrimethoxysilane were then added at 60.degree. C.
and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 1,200 mPas (23.degree.
C.).
Example 2
According to the Invention
In a 2 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 904.5 g of polyether triol built up from propylene
oxide and ethylene oxide (12 wt. %) and having a hydroxyl number of
28.2 mg of KOH/g and 45 wt. % of SAN dispersed therein, and 0.05 g
of dibutyltin dilaurate (Desmorapid.RTM. Z, Bayer MaterialScience
AG) were heated to 60.degree. C. 95.6 g of
3-isocyanatopropyltrimethoxysilane were then added at 60.degree. C.
and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 12,550 mPas
(23.degree. C.).
Example 3
According to the Invention
In a 2 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 902.3 g of polyether triol built up from propylene
oxide and ethylene oxide (13 wt. %) and having a hydroxyl number of
29 mg of KOH/g and 20 wt. % of SAN dispersed therein, and 0.05 g of
dibutyltin dilaurate (Desmorapid.RTM. Z, Bayer MaterialScience AG)
were heated to 60.degree. C. 97.7 g of
3-isocyanatopropyltrimethoxysilane were then added at 60.degree. C.
and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 6,200 mPas (23.degree.
C.).
Example 4
According to the Invention
In a 2 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 902.3 g of polyether triol built up from propylene
oxide and ethylene oxide (13 wt. %) and having a hydroxyl number of
28.5 mg of KOH/g and 20 wt. % of PHD dispersed therein, and 0.05 g
of dibutyltin dilaurate (Desmorapid.RTM. Z, Bayer MaterialScience
AG) were heated to 60.degree. C. 97.7 g of
3-isocyanatopropyltrimethoxysilane were then added at 60.degree. C.
and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 12,500 mPas
(23.degree. C.).
Example 5
According to the Invention
In a 2 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 841.2 g of polyether tetrol started on
ethylenediamine, built up from propylene oxide and having a
hydroxyl number of 50.2 mg of KOH/g and 20 wt. % of SAN dispersed
therein, and 0.05 g of dibutyltin dilaurate (Desmorapid.RTM. Z,
Bayer MaterialScience AG) were heated to 60.degree. C. 158.8 g of
3-isocyanatopropyltrimethoxysilane were then added at 60.degree. C.
and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 4,700 mPas (23.degree.
C.).
Example 6
According to the Invention
In a 2 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 692.5 g of polyether triol started on
triethanolamine, built up from propylene oxide and having a
hydroxyl number of 119 mg of KOH/g and 20 wt. % of SAN dispersed
therein, and 0.05 g of dibutyltin dilaurate (Desmorapid.RTM. Z,
Bayer MaterialScience AG) were heated to 60.degree. C. 307.5 g of
3-isocyanatopropyltrimethoxysilane were then added at 60.degree. C.
and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 2,900 mPas (23.degree.
C.).
Example 7
According to the Invention
In a 2 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, a mixture of 500.0 g of polypropylene glycol having
a hydroxyl number of 112 mg of KOH/g, 500.0 g of polyether triol
built up from propylene oxide and ethylene oxide (12 wt. %) and
having a hydroxyl number of 28.2 mg of KOH/g and 45 wt. % of SAN
dispersed therein, and 0.03 g of dibutyltin dilaurate
(Desmorapid.RTM. Z, Bayer MaterialScience AG) were heated to
60.degree. C. 263.8 g of 3-isocyanatopropyltrimethoxysilane were
then added at 60.degree. C. and the mixture was stirred until the
theoretical NCO content of 0.05% was reached. The excess NCO was
taken up by addition of methanol. The polyurethane polymer
containing alkoxysilane end groups which was obtained had a
viscosity of 1,900 mPas (23.degree. C.).
Example 8
According to the Invention
In a 5 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, a mixture of 1,227.9 g of polypropylene glycol
having a hydroxyl number of 112 mg of KOH/g, 1,227.9 g of polyether
triol built up from propylene oxide and ethylene oxide (12 wt. %)
and having a hydroxyl number of 28.2 mg of KOH/g and 45 wt. % of
SAN dispersed therein, and 0.09 g of dibutyltin dilaurate
(Desmorapid.RTM. Z, Bayer MaterialScience AG) were heated to
60.degree. C. After addition of 130.5 g of
hexamethylene-diisocyanate (Desmodur.RTM. H, Bayer MaterialScience
AG), the mixture was stirred at 60.degree. C. until no further NCO
content was to be detected titrimetrically. 392.4 g of
3-isocyanatopropyltrimethoxysilane were then added at 60.degree. C.
and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 13,800 mPas
(23.degree. C.).
Comparative Example 1
In a 3 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 2,070.3 g of polyether triol built up from propylene
oxide and ethylene oxide (13 wt. %) and having a hydroxyl number of
56 mg of KOH/g and 0.07 g of dibutyltin dilaurate (Desmorapid.RTM.
Z, Bayer MaterialScience AG) were heated to 60.degree. C. 409.2 g
of 3-isocyanatopropyltrimethoxysilane were then added at 60.degree.
C. and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 1,900 mPas (23.degree.
C.).
Comparative Example 2
In a 4 l sulfonating beaker with a lid, stirrer, thermometer and
nitrogen flow, 2,651.7 g of polyether triol built up from propylene
oxide and ethylene oxide (18 wt. %) and having a hydroxyl number of
35 mg of KOH/g and 0.09 g of dibutyltin dilaurate (Desmorapid.RTM.
Z, Bayer MaterialScience AG) were heated to 60.degree. C. 353.2 g
of 3-isocyanatopropyltrimethoxysilane were then added at 60.degree.
C. and the mixture was stirred until the theoretical NCO content of
0.05% was reached. The excess NCO was taken up by addition of
methanol. The polyurethane polymer containing alkoxysilane end
groups which was obtained had a viscosity of 2,100 mPas (23.degree.
C.).
Use Examples
To evaluate the use properties of the various polymers, these were
processed into the following formulation:
TABLE-US-00001 Amount employed in wt. % Polymer 46.06 Filler (Socal
.RTM. U.sub.1S.sub.2) 49.75 Desiccant (Dynasylan .RTM. VTMO) 2.76
Adhesion promoter (Dynasylan .RTM. 1146) 1.38 Catalyst (Lupragen
.RTM. N700) 0.05
For preparation of the formulation, the filler (Socal.RTM. U1S2;
Solvay GmbH) and the desiccant (Dynasylan.RTM. VTMO; Evonik AG) are
added to the polymer as binders and the components are mixed in a
vacuum dissolver with a wall scraper at 3,000 rpm. The adhesion
promoter (Dynasylan.RTM. 1146; Evonik AG) is then added and is
stirred into the mixture at 1,000 rpm in the course of 5 min.
Finally, the catalyst (Lupragen.RTM. N700; BASF SE) is stirred in
at 1,000 rpm and in conclusion the finished mixture is deaerated in
vacuo.
Determination of the Skin Formation Time
A film of the adhesive is applied by means of a doctor blade (200
.mu.m) to a glass plate cleaned beforehand with ethyl acetate, and
is immediately laid in the Drying Recorder. The needle is loaded
with 10 g and moves over a distance of 35 cm over a period of 24
hours.
The Drying Recorder is in a climatically controlled room at
23.degree. C. and 50% rel. atmospheric humidity.
The point in time of disappearance of the permanent trace of the
needle from the film is stated as the skin formation time.
The skin formation time was determined 1 day after the preparation
of the corresponding formulation.
Determination of the Tensile Shear Strength
For determination of the tensile shear strength, singly overlapped
test specimens of beech having an overlapping length of 10 mm are
used. The pieces of beech wood required for this have the following
dimensions: length=40 mm, width=20 mm, thickness=5 mm. The test
specimens are pressed for 24 h at 23.degree. C. and 50% rel.
atmospheric humidity under a pressure of 0.7 N/mm.sup.2 and then
stored for 7 days at 23.degree. C. and 50% rel. atmospheric
humidity, thereafter 20 days at 40.degree. C. and in conclusion one
day at 23.degree. C. and 50% rel. atmospheric humidity.
The tensile shear strength is measured on a tensile tester at speed
of advance of 100 mm/min.
The following table shows the results obtained:
TABLE-US-00002 Comp. 1 Comp. 2 Tensile shear strength [N/mm.sup.2]
8.8 8.0 Skin formation time [min] 45 30 Ex. 1 Ex. 2 Ex. 3 Ex. 4
Tensile shear strength [N/mm.sup.2] 11.0 10.8 11.2 11.6 Skin
formation time [min] 140 20 20 55 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Tensile
shear strength [N/mm.sup.2] 12.2 12.3 12.0 10.9 Skin formation time
[min] 65 60 60 30
The data determined clearly show the superiority of the examples
according to the invention over the comparative examples during
use.
* * * * *